Process for manufacturing motor fuels



Oct. 11, 1938. M. P. YOUKER PROCESS FOR MANUFACTURING MOTOR FUELS Original Filed Feb. 12, 1932 2 Sheets-Sheet 1 v IN VEN TOR M 7 12 A TTORNEYS N. Y B on an I .itohvivn fl t ist nu 22.2.01 nW 3:8 al l b vzzonnu III II b NN N m v Lou- NM Lomu u v ||..|I v a g 2 3 kou aEauut r. I .auflimow 3 1 til. 3 .53.: .36 5. 3 7 LX53 m ute i :0 g S 13 Ma o m0 cu on a m was q Oct. 11, 1938. M. P. YOUKER 2,133,070

PROCESS. FOR MANUFACTURING MOTOR FUELS Original Filed Feb. 12, 1952 2 Sheets- Sheet 2 mmhox.

BY a Q,

v ATTORNEYS.

Patented Oct. 11, 1938 UNITED STATES,

PROCESS FOR MANUFACTURING MO TOR FUELS Malcolm P. Youlrer, Bartlesville, Okla, assignor -to Phillips Petroleum Company, Bartlesville,

kla., a corporation of Delaware I Original application February 12, 1932, Serial No.

Divided and this application February 25, 1936, Serial No. 65,689

2 Claims.

This invention relates to improvements in processes for converting hydrocarbon liquids or gases, and the present application is a division of-my application Serial No. 592,614, filed February 12, 1932.

An object of the invention is to provide a process by which gasoline having a high. antiknock rating and other desirable qualities may be manufactured directly'from crude oil.

Another object is to minimize the losses due to conversion of liquids t9 gases which normally results from the conversion of heavy hydrocarbon liquids to lighter hydrocarbon liquids.

These desirable ends, as well as others, are attained by the process.'

With the foregoing objects outlined and with other objects in view, which will appear as the description proceeds, the invention consists in the novel features hereinafter described in detail, illustrated in the accompanying drawings and more particularly pointed out in the appended claims.

The form of apparatus by which my new process is carriedout is illustrated on the accompanying' drawings.

Figure 1 illustrates in elevation the complete apparatus.

Figure 2 is an elevation of the furnace shown in Figure l, the side wall of the furnace being shown removed and the arrangement of the heating tubes and baflie wallsin the furnace thereby being revealed. f

Figure 3 is a plan view of the furnace 5, the top of which is shown removed thus revealing .the arrangement ofthe baflie walls and heating tubes in theinterior of the furnace.

Crude oil will be delivered through they pipe I into the salt settler 2 which is a horizontal cylindrical tank. A liquid level normall above the center of the salt settler 2 ,will be maintained. Liquid will be delivered from the tank 2 through the pipe 3 by means of the pump 4 through a furnace 5 and into the pipe I. The liquid thus delivered through pipe 3 willbe heated'in passing through the furnace 5 and being delivered into the pipe I will mix with and heat the crude.

from the accumulator 9 through the valved pipe l0. Gases will be vented from the accumulator 9 through the vent pipe ll. Liquid will be withdrawn from the salt settler 2 through a pipe l2 by a pump l3 and will be deliveredby pump I3 through pipe l4 and thence through a heating tube I5 which passes through furnace 5 and delivers into the lower portion of fractionating tower 16. A valve I! which is mounted in heating tube between furnace 5 and fractionating tower It will be utilized to maintain pressure in heating tube l5. Liquid which is passedthrough the heating tube 15 will be heated therein and will, upon entry into the fractionating tower 16, to a large extent, vaporize, and the vapors thus generated will-flow upward through the fractionating tower I6 and bubble trays l8, and thence through pipe 19 and condenser 29 and pipe 2 I into the gas-liquid separator 22.

Gas which will accumulate in the separator 22 in gaseous. condition will -be vented therefrom through the pipe 23 in which is mounted a valve 24. A part of the gas which will accumulate in liquid state in the separator 22 will be pumped therefrom-through the pipe 25 by means of the pump 26 into and through heating tube I 5. A part of the liquefied gas which will accumulate in the separator 22 will be delivered thence by pump 21 through pipe 28 in which is mounted valve 29 into the top of fractionating tower l3. As a result of delivering said liquid through pipe 23 into the top of fractionating tower l6, liquid reflux will flow downward through fractionating tower 16 over bubble trays l8 and will contact and condense a portion of the vapors which will rise through fractionating tower l6, and as a result of said condensation, liquid, consisting of gasoline and heavier fluid, will accumulate in the fractionating tower l6. Liquid which will collect in the bottom of fractionating tower 16 will flow thence through pipe 28' in which is mounted a valve 29 into a fractionating tower 30 at a point belowthebubble trays 3| which aremo'imted. in fractionating tower 30. 7

Pressure will be maintained in fractionating tower, IS in excess of the pressure which will be maintainedin the fractionating tower 30, and,

as a result, liquid flowing from fractionating tower l6 through pipe 28' into fractionating tower 30, will partially vaporize upon entry into fractionating tower 30, and vapors thus generated will flow upward through bubble plates 3| in fractionating tower 39, and thence through pipe 32, clay treater 33, pipe 34, and condenser. 35. Condensate, will flow from condenser 35 through pipe 36 into accumulator 31. M

A suflicient quantity of the liquid which will gather in the accumulator 3] will be pumped therefrom through pipe 38 by means of pump 39 into the top of fractionating tower 30 to maintain a. temperatureat the top of'fractionating tower 30 such that only gasoline vapors will pass therefrom to the condenser 35. Thus gasoline onlywill be delivered into the accumulator 31.

Gasoline will be withdrawn from accumulator I 31 through the pipe 40 in which is mounted valve through a pipe 43 in which is mounted a valve 44.

Distillate will be deliveredby a pumpv45 from one of the bubble plates 3| through a pipe 46 which will pass through furnace 5 and lead into the pipe 28'. 1

The liquid which will be passed throughpipe 46 will be heated in passage through furnace 5 and will, upon entry into the pipe 28',heat the liquids which will flow from the fractionating tower l6 through the pipe 28'.

Fuel oil will be withdrawn from the bottom of fractionating tower 30 through pipe 41 in which is mounted valve 48. A pipe 1 49 in which is mounted a valve 50 will serve to conduct liquid from an-intermediate one of the bubble trays l8 in fractionating tower l6 into fractionating tower 30 at a point above the entry point of pipe 28' into fractionating tower 30.,

A conventional caustic washer 5| is mounted in fuel oil, hydrogen, or any other hydrocarbon ma-.'

terial or treating agent may be introduced into and passed through the heating tube I5. I may elect to deliver gasoline collected in the accumulator 9 and into and through the heating tube l5 by means of the pump 56 and the valved pipe Water or water containing treating agents, either in suspension or in solution, or treating agents alone, may be introduced through valved pipe tliinto the heated hydrocarbon which will flow from the furnace through heating tulbe I5 into fractionating tower l6.

Crude oil being preheated and delivered into salt settler 2 will flow slowly through this salt settler and any salt contained in the crude, as well as other debris, will be settled from the crude therein and will be periodically removed.-

A body of fullers earth will be so disposed in the clay treater 33 that vapors-may readily flow through this body of clay and intimately contact the particles thereof. Polymerized hydrocarbon liquids which will be formed in the clay treater 33 as a result of the contact between vapors and fullers earth therein, will be withdrawn therefrom through a pipe 52 in which is mounted a valve 53. These polymerized hydrocarbons may either be withdrawn to storage or theymay be,

delivered by means of a pump 54 which is mounted in a pipe 55 into fractionating column 30.

The pressure maintained in the salt settler 2 will be only that which is set up therein by resistance to flow of vapors through the pipe 6 and the condenser 1. Although good results may be ob'- and said pumps.

tained at lower pressures, I=wi1l preferably maintain a pressure of approximately 3000 pounds per square inch in the heating tube l5. Normally the pressure set up at the discharge of the pumps 3 ing tower IS, the separator 22, the condenser 20,

and inter-connecting pipes.

' The pressure maintained in the fractionating column 30,.the clay treater 33, condenser 35 and inter-connecting lines. will be only in excess of atmospheric pressure, to the extent'that pressure is set up by reason of the resistance to flow of vapors and condensate through this system, as the accumulator 31 will be operated at approximately atmospheric pressure.

The length of that part of .the pipe 3 which will be exposed to heatin the furnace 5 will be so proportioned that the liquid which will enter the salt settler 2 will be heated toabout 250 F. Therefore, nothing heavier than gasoline will be vaporized in the salt settler 2.

By regulation of the quantity of fuel fired in the furnace 5, the temperature to which the liquid passed through heating tube l5 will be heated will vary between 800 F. and 900 F. andthis temperature will preferably bebe 11 345 F. and 865 F. The temperature nia ed at the top of the fractionating tower' is byihans of regulating the delivery of reflux liquid into the top of this towerwill be such that the vapor pressure of the liquid leaving the bottom of this fractionating tower will be in accord with the current specifications for motor fuel, which at this time vary between 8 pounds per square inch and 13 pounds per square inch when taken by the Reid method at 100 F. That part of the pipe 46 which will be exposed to heat in the furnace 5 will be so proportioned that the bottom of thefractionating tower 30 will be heated to the extent necessary to remove from the liquidswhich will collect in the bottom of fractionating tower .30 practically all gasoline fractions.

The heating tube l5 a heating portion and a conversion portion after the manner which has already been disclosed in applications for patent filed by the present applicant 'to conversion temperatures in the first partof the heating tube l5 and then pass' the thus heated material through a latter portion of the heating tube I5which is so arranged in the furnace as to be only mildly heated.

Referring to Figures 2*and 3 of the drawings, it

"will be noted that the interior of the furnace 5 is so partitioned off by abridge wall GI and a baflle wall 62 that a combustion chamber is formed between bridge wall gland the end wall 69-0f the furnace and that gases of combustion developed in this combustion chamber are restricted to flow upward over the top of bridge wall 6| thence downward through a passageway between bridge wall 6| andbaflie wall 62 thence under baflle wall 62 and thence upward through a passageway between bridge wall 62 and the adjacent end wall 10 of the furnace and thence through a breeching 63 in which is mounted a damper 64 and thence upward through a smoke tween the bottom of said last-mentioned passageway between said baflle wall and said adjacent end wall and the bottomof said smoke stack 66.

The fan 61 may be operated to force gases of combustion from the smoke stack into the furnace, thus recirculating gases of combustion through 'said last-mentioned passageway, or said fan may be allowed to remain stationary in whichcase gases of combustion-will flow from the furnace I into the smoke stack through the breeching 66,

and in either case the damper 68 may be used to regulate the flow of gases. of combustion through the breeching. 66. Temperature recording devices not shown on the drawings are of course installed'at the junction of the heating portion and the conversion portion and at the outlet of the heating tube l to indicate and record the temperature of material passing through the heating tube at these points. The heating tube I5 is made' up of a plurality of horizontal tubes interconnected by means of return bends in a conventional manner and is supported in the furnaceby conventional tube sheets which are not shown That portion of the heating tube l5 which is utilized for the rapid heating of the materials passed therethrough to conversion temperature is so disposed over the combustion chamber and in the passageway between bridge wall 6.] and bailie wall That portion of thepipe 46 which passes through positionbelow the heating portion of the heating tuberl5. That portion of the pipe 3 which passes,

the furnace 5 is disposed in the passageway be-' tween bridge wall-6| and baflle wall 62 and in 'a through furnace 5 is disposed in the passageway between the baifle wall 62 and the adjacent end wall 10,0f the furnace in a position above the conversion portion of the heating tube [5.

It will beseen that the flow of gases of combustion through the furnace 5 is such that these gases first contact the heating portion of the heating tube l5;- second, contact that portion of the pipe 46 which passes through the furnace 6; third, contact the conversion portion of the .heating tube l5: and, fourth, contact that part of the" pipe'3 which passes through the furnace 5.1 The quantity of liquid which will be pumped through the pipe 46 will be so regulated and the length and size of that portion 'of thepipe 46 which is disposed in the furnace 5 will be so proportioned as to reduce the temperature of the gases of combustion passing around the pipe 46 to any desired temperature before these gases contact the conversion portion of the heating tube i5. Increasing the flow of oil through pipe 46 wilL cool the gases of combustion passing over the conversion portion of the heating tube l6 to any desired temperature and in this way heattransfer from the gases of combustion to the conversion portion of the heating tube I 6 may be caused to take place at a low rate and the quantity of heat so transferred may be regulated. It is apparent that some other stream of liquid might be passed through the pipe 46 to accomplish this purpose and that my reasons for using the particular stream of liquid designated are economic.

The manner in which the breeching 66, together with the fan 61 and the damper 66, may be advantageously used to abstract gases of combustion from the furnace before the same have passed over the conversion portion of the heat- .ing tube II or to force recirculation of gases from the smoke stack back into the furnace and over said conversion portion of said tube is already disclosed in the above-mentioned patent application Serial No. 579,044, previously filed by the present applicant.

Circulating gases of combustion from the bot- I tom of the smoke stack 66 by means of the fan permitting regulated moderate heating of the materials passing through the conversion portion of heating tube l6. Withdrawing gases of combustion in 'regulated quantities from the furnace 6'into smoke stack 66 through the breeching 66 will result in regulating the quantity of gases of combustion which will flow over the conversion an economic arrangement the principally advantageous feature of the furnace and heating arrangement shown is. that the gases of combustion after being contacted with the heating portion of the heating tube II are cooled by being contacted with the heating pipe 46 before being contacted with the conversion portion of the heating tube I6 thus permitting mild'heating of'said conversion 'portion of said tube.

The materials passed through the heatingtube [6 should be heated in passingitherethrough to a maximum temperature in the heating portion of this tube and the temperature of these materials should not thereafter be increased in passing through the conversion portion of the tube. In

other words, a portion of the hating tube l6 adiacent'to'the exit end of said tube should beheated in a manner such that only heat absorbed by the conversion reaction is supplied to the materials flowing therethrou'gh and such that the temperature of suchv materials is not increased in passing through thislatter portion 'of said heattube is should be of substantial length. While some results may be obtained by using a three inch inside diameter tube as short as 500 feet,it is desirable to use a three inch inside diameter ing -tube. The conversion portion of the heating tube at,least 2000 feet 1038, and preferably 3000 or M00 feet long, for conversion j purposes, through which the material to be converted is flawed after such material has been brought 'to conversion temperature. While I have described the desirable conditions which should boobtained in the conversion portion of the heating tube I5, I would say that in order to obtain results sufiiciently practical to permit commercial operation it is absolutely necessary that not less ihan the latter 500 linear feet or" the heating tube I5 be supplied with heat in quantity such that the temperature of the materials passing there-' through be raised not more than two degrees Fahrenheit per 100 feet of travel through said latter portion of heating tube ,l5 and as stated above heat should preferably be supplied to the materials passing through the latter portion of said heaing tube in considerably less than this quantity.

The maximum advantageous tempera ure to be used will be found to vary with the type of material undergoing conversion. I have constructed and have in operation two heating tubes similar to the heating tube I5 herein described, one of which, is used for the conversion of heavy fuel oil to gasoline and gas oil and one of which is used for converting gasoil to gasoiine. I-find that maintaining temperatures of approximately 850 F. and 840 F., respectively, at the inlet and the outlet of the conversion portion of the heating tube obtains very good results in the conversion or the fuel oil when operated under a pressure of about 350v pounds per square inch, while for the advantageous conversion of gas oil temperatures of approximately 885 F. and 375 K, respectively, maintained at the iniet and outlet of the conversion portion of the heating tube appear to be the best temperatures when operating under about 350 pounds per square inch pressure. It should be noted that while the present process is specifically outline-:1, for and appears'to be particularly advantageous for the conversion of crude oiis the process may also be advantageously utilized for the conversion of other oils such as fuei oil or gas oil.

It appears that the conversion of oils, which already conain gasoline, to gasoline may be accomplished particularly by the combination of steps outlined herein; that is, by passing the same through the heating tube iii in the manner described under a pressure upwards of 1500 pounds per square inch particularly in that the an'iknock rating of the gasoline as a whole thus is to be understood that I do not intend to limit my claims to these detailsbut intend to claim broadly aii of the advantages which are-inherent in this process. I

What I claim and desire-to secure by Letters Patent isi Y Lin a process of the character described, in producing thermally conrerted hydrocarbons in heated condition into the lower portioniof a first rectification zone mainain'ed under relativelyhigh sup-eratmospheric pressure, rectifying said hydrocarbons in said zone and thereby effecting V a relatively sharp separation between normally gaseous hydrocarbons and normally liquid hydrocarbons, discharging said normally gaseous hydrocarbons from the upper portion of said zone and cooling and condensing some of ,thesame,

returning some of said condensate in liquefied condition into the upper portion of said recti-, fication zone for refluxing said zone, dividing said normally liquid hydrocarbons into a plurality of streams and after releasing the pressure on the same introducing these streams at different elevations into a second rectification zone maintained under substantially atmospheric pressure, heating the lower portion of the second rectification zone by withdrawing a portion of the normally liquid hydrocarbons, heating the withdrawn portion and returning the same to the lower portion of the second rectification zone, rectifying the normally liquid hydrocarbons in the second rectifying zone and thereby separating hydrocarbons in the gasoline range from heavier hydrocarbons,- discharging the hydrocarbons in the gasoline range from the upper portion of the second rectification zone and condensing the same, returning'a portion or the resulting condensate into the upper portion of the second rectification zone as a reflux, and withdrawing hydrocarbons heavier than gasoline from the second rectification zone.

2. In a process for converting hydrocarbon fluids in which the fluid is subjected to pressure conversion in a conversion zone from which the resulting mixture is removed, the improvement which comprises rectifying said. mixture in a first rectification zone under a pressure sufiicient to maintain some of the normally gaseous components of the mixture in liquefied condition, discharging normally gaseous components from the top of said rectification zone and cooling the same to condense a heavier portion of said nor-' mally gaseous components, then passing said gaseous components into a separating zone and separating the condensate from the uncondensed portion, discharging the uncondensed portion from said separating zone, passing a portion of i said condensate from the separating zone into the upper portion of said rectification zone and using it as a reflux to prevent normally liquid hydrocarbons from leaving the upper portion of said rectification zone, passing another portionof said condensate in liquid condition to the inlet of the conversion zone, passing a light liquid fraction from the medial portion of said rectification zone into the medial portion of a second rectification zone maintained under lower pressure, passing a heavier liquid fraction from the lower portion of the first rectification zone into the lower portion of the second rectification zone, withdrawing a distillate streamfrom the second rectification zone at a point between the points where the liquid fractions are'introduced into the same, reheating said distillate stream and mixing it with said heavier liquid fraction before the latter enters the second rectification zone, whereby the lower portion of ,the second rectification zone is heated sufiiciently to cause portion of the second rectification zone as a reflux. 1 LiALCOIM P. YQUKER. 

